Progress in Energy and Combustion Science 30 (2004) 219230 www.elsevier.

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Combustion characteristics of different biomass fuels

Ayhan Demirbas*
Department of Chemical Engineering, Selcuk University, Konya, Turkey Received 15 March 2003; accepted 31 October 2003

Abstract Biomass energy is one of humanitys earliest sources of energy particularly in rural areas where it is often the only accessible and affordable source of energy. Worldwide biomass ranks fourth as an energy resource, providing approximately 14% of the worlds energy needs all human and industrial processes produce wastes, that is, normally unused and undesirable products of a specic process. Generation and recovery of solid wastes varies dramatically from country to country and deserves special mention. The burning velocity of pulverized biomass fuels is considerably higher than that of coals. The use of biomass fuels provides substantial benets as far as the environment is concerned. Biomass absorbs carbon dioxide during growth, and emits it during combustion. Utilization of biomass as fuel for power production offers the advantage of a renewable and CO2-neutral fuel. Although the structural, proximate and ultimate analyses results of biomass and wastes differ considerably, some properties of the biomass samples such as the hydrogen content, the sulfur content and the ignition temperatures changed in a narrow interval. q 2004 Elsevier Ltd. All rights reserved.
Keywords: Biomass; Combustion; Fuel properties; Coring

Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1. Biomass sources. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2. Current biomass conversion technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Solid wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Gasication of biomass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Steam reforming of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Gasication systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4. Pyrolysis of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5. Fuel properties of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6. Combustion properties of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1. The chemistry of biomass combustion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2. Some combustion properties of selected biomass samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3. Calculation of higher heating value. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7. Coring of biomass and coal blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.1. Co-pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2. Mechanism of biomass coring with coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

220 220 220 220 221 221 222 222 222 224 225 225 226 227 227 228 228 229

* Corresponding author. Tel.: 90-462-230-7831; fax: 90-462248-8508. E-mail address: ayhandemirbas@hotmail.com (A. Demirbas). 0360-1285/$ - see front matter q 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.pecs.2003.10.004

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1. Introduction Biomass can be converted into liquid, solid and gaseous fuels with the help of some physical, chemical and biological conversion processes [1,2]. The conversion of biomass materials has a precise objective to transform a carbonaceous solid material which is originally difcult to handle, bulky and of low energy concentration, into the fuels having physico chemical characteristics which permit economic storage and transferability through pumping systems. Worldwide biomass ranks fourth as an energy resource, providing approximately 14% of the worlds energy needs; biomass is the most important source of energy in developing nations, providing; 235% of their energy [3,4]. The use of biomass fuels provides substantial benets as far as the environment is concerned. Biomass absorbs carbon dioxide during growth, and emits it during combustion. Therefore, biomass helps the atmospheric carbon dioxide recycling and does not contribute to the greenhouse effect. Biomass consumes the same amount of CO2 from the atmosphere during growth as is released during combustion. 1.1. Biomass sources Biomass fuels potential includes wood, short-rotation woody crops, agricultural wastes, short-rotation herbaceous species, wood wastes, bagasse, industrial residues, waste paper, municipal solid waste, sawdust, bio-solids, grass, waste from food processing, aquatic plants and algae animal wastes, and a host of other materials. Animal wastes are another signicant potential biomass resource for electricity generation, and like crop residues, have many applications, especially in developing countries. Biomass is only organic petroleum substitute which is renewable. Biomass offers important advantages as a combustion feedstock due to the high volatility of the fuel and the high reactivity of both the fuel and the resulting char. However, it should be noticed that in comparison with solid fossil fuels, biomass contains much less carbon and more oxygen and has a low heating value. The burning velocity of pulverized biomass fuels is considerably higher than that of coals. The pulverized biomass fuels can be burned in a ame in the same way as oil or gas fuels and at the same high power output [5]. 1.2. Current biomass conversion technologies Direct combustion is the old way of using biomass. Biomass thermo-chemical conversion technologies such as pyrolysis and gasication are certainly not the most important options at present; combustion is responsible for over 97% of the worlds bio-energy production. Some processes such as pyrolysis, gasication, anaerobic digestion and alcohol production have widely been applied to biomass in order to obtain its energy

content. Biomass can be directly red in dedicated boilers. However, coring biomass and coal has technical, economical, and environmental advantages over the other options. Coring biomass with coal, in comparison with single coal ring, helps reduce the total emissions per unit energy produced. The oldest of all fuels, wood (or biomass), and the old original fuel of the industrial revolution, coal, are key to this move to a new mission. Technical issues that can lead to doubt about of biomass coring with coal are being resolved through testing and experience [6]. Main current biomass technologies are [7]: 1. Destructive carbonization of woody biomass to charcoal 2. Gasication of biomass to gaseous products 3. Pyrolysis of biomass and solid wastes to liquid, solid and gaseous products 4. Supercritical uid extractions of biomass to liquid products 5. Liquefaction of biomass to liquid products 6. Hydrolysis of biomass to sugars and ethanol 7. Aneorobic digestion of biomass to gaseous products 8. Biomass power for generating electricity by direct combustion or gasication and 9. pyrolysis 10. Coring of biomass with coal 11. Biological conversion of biomass and waste (biogas production, wastewater treatment) 12. Biomass densication (briquetting, pelleting) 13. Domestic cookstoves and heating appliances of fuelwood 14. Biomass energy conservation in households and industry 15. Solar photovoltaic and biomass based rural electrication 16. Conversion of biomass to a pyrolytic oil (biofuel) for vehicle fuel 17. Conversion of biomass to methanol and ethanol for internal combustion engines In earlier work [8], ground biomass samples have been converted completely into water insoluble and soluble chemicals in the presence of anhydrous glycerin with alkali such as Na2CO3 or KOH. The acetone solubles from acidication of the liquefaction products was called biofuel in this study. The solubility of the biofuel in gasoline was tested as 1.96% by weight. In another work [9], the acetone solubles of the pyrolysis products from the biomass samples were added to gasoline.

2. Solid wastes The waste products of a home include paper, containers, tin cans, aluminium cans, and food scraps, as well as sewage.

A. Demirbas / Progress in Energy and Combustion Science 30 (2004) 219230 Table 1 Contents of domestic solid waste (Percentage of total) Component Paper waste Food waste Plastic matter Metal Glass Textile Wood Leather and rubber Miscellaneous Source: Ref. [48]. Lower limit 33.2 18.3 7.8 7.3 8.6 2.0 1.8 0.6 1.2 Upper limit 50.7 21.2 11.2 10.5 10.2 2.8 2.9 1.0 1.8

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Table 2 Generation and recovery of MSW in the US, 1993 (million tons) Material Generation Recovered Discarded Projected generated 2000 24.0 2.7 4.7 0.6 0.4 0.6 1.2 0 5.9 0 0.6 40.7 46.6 9.7 10.8 16.9 5.4 4.9 11.2 12.5 23.9 2.8 2.4 147.1 81.0 12.7 17.2 20.4 6.9 5.6 14.5 12.7 20.1 3.0 3.2 197.3

The waste products of industry and commerce include paper, wood, and metal scraps, as well as agricultural waste products [10,11]. Biodegradable wastes, such as paper nes and industrial biosludge, into mixed alcohol fuels (e.g. isopropanol, isobutanol, isopentanol). The wastes are rst treated with lime to enhance reactivity; then they are converted to volatile fatty acids (VFAs) such as acetic acid, propionic acid, and butyric acidusing a mixed culture of microorganisms derived from cattle rumen or anaerobic waste treatment facilities. Pulp and paper wastes may also be treated to produce methane. The contents of domestic solid waste are given in Table 1. There are four major methods for conversion of organic wastes to synthetic fuels: (1) hydrogenation; (2) pyrolysis; (3) gasication: and (4) bioconversion [12]. The rst three have been advanced to the pilot-plant stage, while the fourth has been the subject of only minor research effort, but is a long term possibility. Typical solid wastes include wood material, pulp and paper industry residues, agricultural residues, organic municipal material, sewage, manure, and food processing by-products. Biomass is considered one of the main renewable energy resources of the future due to its large potential, economic viability and various social and environmental benets. It was estimated that by 2050 biomass could provide nearly 38% of the worlds direct fuel use and 17% of the worlds electricity [13]. If biomass is produced more efciently and used with modern conversion technologies, it can supply a considerable range and diversity of fuels at small and large scales. Municipal solid waste (MSW) is dened as waste durable goods, nondurable goods, containers and packaging, food scraps, yard trimmings, and miscellaneous inorganic wastes from residential, commercial, and industrial sources. Generation refers to the amount of material that enters the waste stream before recovery, composting, or combustion. Recovery refers to materials removed from the waste stream for the purpose of recycling and/or composting. Table 2 shows the generation and recovery of MSW in the US in 1993. The energy content of MSW in the US is typically from 10.5 to 11.5 MJ/kg. The generation and recovery of MSW varies dramatically from country to

Paper 70.5 Glass 12.4 Metals 15.5 Plastics 17.5 Rubber/leather 5.6 Textiles 5.5 Wood 12.4 Food 12.5 Yard trimmings 29.8 Misc. organic 2.8 Others 3.0 Total 187.5 Source: Ref. [49].

country and deserves special mention. For example, recent estimates indicate MSW generation in the UK of about 30 million tons of which 90% is landlled. In comparison, Sweden landlled only 34% of their MSW generation [14].

3. Gasication of biomass Gasication is a form of pyrolysis, carried out at high temperatures in order to optimize the gas production. The resulting gas, known as producer gas, is a mixture of carbon monoxide, hydrogen and methane, together with carbon dioxide and nitrogen. Biomass gasication technologies have historically been based upon partial oxidation or partial combustion principles, resulting in the production of a hot, dirty, low caloric value gas that must be directly ducted into boilers or dryers. In addition to limiting applications and often compounding environmental problems, these technologies are an inefcient source of usable energy. Biomass gasication is the latest generation of biomass energy conversion processes, and is being used to improve the efciency, and to reduce the investment costs of biomass electricity generation through the use gas turbine technology. High efciencies (up to about 50%) are achievable using combined-cycle gas turbine systems, where waste gases from the gas turbine are recovered to produce steam for use in a steam turbine. Economic studies show that biomass suffocation plants can be as economical as conventional coal-red plants. 3.1. Steam reforming of biomass Most biomass gasication systems utilize air or oxygen in partial oxidation or combustion processes These processes suffer from low thermal efciencies and low caloric

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gas because of the energy required to evaporate the moisture typically inherent in the biomass and the oxidation of a portion of the feedstock to produce this energy. The prosess of synfuels from biomass will lower the energy cost, improve the waste management and reduce harmfull emissions. This triple assault on plant operating challenges is a proprietary technology that gasies biomass by reacting it with steam at high temperatures to form a clean burning synthesis gas (called as the syngas, hydrogen and carbon monoxide in a 2 to 1 ratio). The molecules in the biomass (primarily carbon, hydrogen and oxygen) and the molecules in the steam (hydrogen and oxygen) reorganize to form this syngas [7]. 3.2. Gasication systems Gasication for power production involves the devolatilization and conversion of biomass in an atmosphere of steam and/or air to produce a medium or low caloric value gas. If air is present, the ratio of oxygen to biomass is typically around 0.3. A large number of variables affect gasication based process design. Gasication medium is an important variable. Air blown or directly heated gasiers, use the exothermic reaction between oxygen and organics to provide the heat necessary to devolatilize biomass and to convert residual carbon-rich chars. Commercial gasiers are available in a range of size and types, and run on a variety of fuels, including wood, charcoal, coconut shells and rice husks. Power output is determined by the economic supply of biomass, which is limited to 80 MW in most regions. The biomass gasication process is similar to processes used for many years by chemical and petrochemical manufacturers, including methanol, ammonia and ethylene producers. In these chemical processes, natural gas or another hydrocarbon is reformed into a more desirable gaseous chemical feedstock by reacting it with steam at elevated temperatures. The hydrogen and oxygen molecules in the steam are liberated and a series of reactions result in a reorganization of the compounds to form synthesis gas (primarily H2, CO and CO2). This synthesis gas is then catalytically converted into methanol, ammonia or another product.

In pyrolysis process, biomass converts into liquid (biooil or bio-crude), charcoal and non-condensable gasses, acetic acid, acetone, and methanol by heating the biomass to about 750 K in the absence of air. The process can be adjusted to favor charcoal, pyrolytic oil, gas, or methanol production with a 95.5% fuel-to-feed efciency. Pyrolysis can be used for the production of bio-oil if ash pyrolysis processes are used and are currently at pilot stage [16]. Some problems in the conversion process and use of the oil need to be overcome; these include poor thermal stability and corrosivity of the oil. Upgrading by lowering the oxygen content and removing alkalis by means of hydrogenation and catalytic cracking of the oil may be required for certain applications [12]. Pyrolysis of wood has been studied as a zonal process [17]. Thermal degradation properties of hemicelluloses, celluloses and lignin can be summarized as follows [18]: Thermal degradation of hemicelluloses . of cellulose . of lignin Pyrolysis of biomass is thermal decomposition of the fuel. As with coal, pyrolysis is a relatively slow chemical reaction occurring at low temperatures. The reaction mechanisms of biomass pyrolysis are complex but can be dened in ve stages for wood [19]: 1. 2. 3. Moisture and some volatile loss. Breakdown of hemicellulose; emission of CO and CO2. Exothermic reaction causing the woody biomass temperature to rise from 525 to 625 K; emission of methane, hydrogen and ethane. External energy is now required to continue the process. Complete decomposition occurs.

4. 5.

5. Fuel properties of biomass The limitations were primarily due to relying on biomass as the sole source of fuel, despite the highly variable properties of biomass. The high moisture and ash contents in biomass fuels can cause ignition and combustion problems. The melting point of the dissolved ash can also be low which causes fouling and slagging problems. Because of the lower heating values of biomass accompanied by ame stability problems. It is anticipated that blending biomass with higher quality coal will reduce ame stability problems, as well as minimize corrosion effects. The methods of biomass fuel analyses are given in Table 3. Biomass offers important advantages as a combustion feedstock due to the high volatility of the fuel and the high reactivity of both the fuel and the resulting char. However, it should be noticed that in comparison with solid fossil fuels, biomass contains much less carbon and more oxygen and has a low heating value. Also, chlorine contents of certain biofuels, like straw can exceed the level

4. Pyrolysis of biomass Pyrolysis is dened as the thermal destruction of organic materials in the absence of oxygen. Pyrolysis is the basic thermochemical process for converting biomass to a more useful fuel [15]. Biomass is heated in the absence of oxygen, or partially combusted in a limited oxygen supply, to produce a hydrocarbon rich gas mixture, an oil-like liquid and a carbon rich solid residue.

A. Demirbas / Progress in Energy and Combustion Science 30 (2004) 219230 Table 3 Methods of biomass fuel analyses Property Heating value Particle size distribution Proximate composition Moisture Ash Volatile matter Fixed carbon Ultimate elemental Carbon, hydrogen Nitrogen Sulfur Chlorine Oxygen Ash elemental Analytical method ASTM D 2015, E 711 ASTM E828 ASTM E871 ASTM D1102 (873 K), ASTM E830 (848 K) ASTM E 872, ASTM E 897 by difference ASTM E 777 ASTM E 778 ASTM E 775 ASTM E776 By difference ASTM D3682, ASTM D2795, ASTM D4278, AOAC 14.7 Table 5 Structural analyses of selected biomass samples (wt. % daf) Fuel sample

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Hemicelluloses Cellulose Lignin Extractive matter a 30.4 39.4 23.6 31.2 20.7 31.0 19.9 22.7 28.9 34.6 26.8 28.8 24.0 45.3 49.8 50.5 30.2 25.6 50.7 48.4 42.9 18.6 48.4 21.9 27.0 15.0 40.0 52.3 20.4 17.0 3.3 9.4 1.6 2.5 3.5 9.9 2.8 2.5 2.7

Hazelnut shell Wheat straw Olive husk Beech wood Spruce wood Corncob Tea waste Walnut shell Almond shell Sunower shell
a

Source: Ref. [32]. Alcohol/benzene (1/1, v/v) extractives.

of coal. In the combustion applications, biomass has been red directly either alone or along with a primary fuel. Chlorine, which is found in certain biomass types, such as straw, may affect operation by corrosion. The high chlorine and alkali content of some biomass fuels raise concerns regarding corrosion. The greatest concern focuses on hightemperature corrosion of super-heater tubes induced by chlorine on the surface. Biomass differs from coal in many important ways, including the organic, inorganic, energy content, and physical properties. Relative to coal, biomass generally has less carbon, more oxygen, more silica and potassium, less aluminum and iron, lower heating value, higher moisture content, and lower density and friability (Table 4). The point on the burning prole at which the rate of weight loss due to combustion is a maximum called as peak
Table 4 Physical, chemical and fuel properties of biomass and coal fuels Property Fuel density (kg/m3) Particle size C content (wt% of dry fuel) O content (wt% of dry fuel) S content (wt% of dry fuel) SiO2 content (wt% of dry ash) K2O content (wt% of dry ash) Al2O3 content (wt% of dry ash) Fe2O3 content (wt% of dry ash) Ignation temperature (K) Peak temperature (K) Friability Dry heating value (MJ/kg) Biomass ,500 ,3 mm 42 54 35 45 Max 0.5 23 49 4 48 2.4 9.5 1.5 8.5 418 426 560 575 Low 14 21 Coal ,1300 ,100 mm 6585 215 0.57.5 4060 26 1525 818 490595 High 2328

temperature. The burning prole peak temperature is usually taken as a measure of the reactivity of the sample. The peak temperatures for biomass samples generally vary from 560 to 575 K. The structural analyses of selected biomass samples are given in Table 5. The ultimate analyses of typical fuel samples given in the literature and determined are shown in Tables 6 and 7, respectively. It is difcult to establish a representative biomass due to large property variations, but two examples are included here for comparison. The composition variations among biomass fuels are larger than among coals, but as a class biomass has substantially more oxygen and less carbon than coal. Less obviously, nitrogen, chlorine, and ash vary signicantly among biomass fuels. These components are directly related to NOx emissions, corrosion, and ash deposition. Biomass generally has relatively low sulfur compared to coal. The proximate analyses of selected biomass samples given in the literature and determined as dened by ASTM are shown in Tables 8 and 9, respectively. The inorganic properties of selected fuel samples are given in Table 10. Inorganic components in coal vary by rank and geographic
Table 6 Ultimate analyses of typical fuel samples given in the literature (wt % of dry fuel with ash) Fuel sample Hazelnut shell Sawdust Corn stover Poplar Rice husk Cotton gin Sugarcane bagasse Peach pit Alfafa stalk Switchgrass C 52.8 46.9 42.5 48.4 47.8 42.8 44.8 53.0 45.4 46.7 H 5.6 5.2 5.0 5.9 5.1 5.4 5.4 5.9 5.8 5.9 N 1.4 0.1 0.8 0.4 0.1 1.4 0.4 0.3 2.1 0.8 S 0.04 0.04 0.2 0.01 0.5 0.01 0.05 0.09 0.19 O (diff.) 42.6 37.8 42.6 39.6 38.9 35.0 39.6 39.1 36.5 37.4 Reference [32,57] [50] [51] [52] [53] [54] [52] [52] [55] [55]

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A. Demirbas / Progress in Energy and Combustion Science 30 (2004) 219230 Table 9 Proximate analyses of selected biomass samples (wt % of dry fuel) Fuel sample Beech wood bark Oak wood Wheat straw Olive husk Beech wood Spruce wood Corncob Tea waste Walnut shell Almond shell Sunower shell Colza seed Pine one Cotton refuse Olive refuse Ash 5.7 0.5 13.7 4.1 0.5 1.7 1.1 1.5 2.8 3.3 4.0 6.5 1.0 6.6 9.2 Volatile matter 65.0 77.6 66.3 77.5 82.5 80.2 87.4 85.5 59.3 74.0 76.2 78.1 7.3 81.0 66.1 Fixed carbon 29.3 21.9 21.4 18.4 17.0 18.1 11.5 13.0 37.9 22.7 19.8 15.4 21.7 12.4 24.7

Table 7 Ultimate analyses of typical fuel samples (wt % of dry fuel with ash) Ful sample Coal type 1 Red oak wood Wheat straw Olive husk Beech wood Spruce wood Corncob Tea waste Walnut shell Almond shell Sunower shell C 81.5 50.0 41.8 49.9 49.5 51.9 49.0 48.0 53.5 47.8 47.4 H 4.0 6.0 5.5 6.2 6.2 6.1 5.4 5.5 6.6 6.0 5.8 N 1.2 0.3 0.7 1.6 0.4 0.3 0.5 0.5 1.5 1.1 1.4 S 3.0 0.05 0.2 0.06 0.1 0.06 0.05 Cl 1.5 0.2 0.1 0.1 0.1 0.1 O (diff.) 3.3 42.4 35.5 42.0 41.2 40.9 44.5 44.0 45.4 41.5 41.3

Source: Refs. [32,34].

region. As a class, coal has more aluminum, iron, and titanium than biomass. Biomass has more silica, potassium, and some times calcium than coal. The wood and woody materials tend to be low in nitrogen and ash content while the agricultural materials can have high nitrogen (Tables 6 and 7) and ash contents (Tables 8 and 9). Straw may have a high content of chlorine and potassium, elements which are very undesirable in power plant fuels. Levels of K2O and Cl were found as 20.0 and 3.6% in ash, respectively, in wheat straws (Table 10). A pretreatment process to remove potassium from straw fuel may be based on pyrolysis followed by char wash. The straw is pyrolyzed at moderate temperatures at which the potassium is retained in the char. Potassium and residual chlorine are extracted from the residual char by water [20]. Char and pyrolysis gases may then be used in a conventional boiler without problems due to the high straw potassium content. To evaluate this pretreatment process knowledge about the char wash process is needed. Alkalis, when reacted with sulfates and chlorine, may harm thermochemical conversion systems, fouling heat exchange surfaces, gas-turbine blades, and other power system components [21].
Table 8 Proximate analyses of selected biomass given in the literature (wt % of dry fuel) Fuel sample Ash Volatile matter 76.3 82.2 84.0 61.0 76.1 76.7 Fixed carbon Reference

Source: Refs. [30,32,34].

6. Combustion properties of biomass In general combustion models of biomass can be classied as macroscopic or microscopic. The macroscopic properties of biomass are given with for macroscopic analysis, such as ultimate analysis, heating value, moisture content, particle size, bulk density, and ash fusion temperature. Properties for microscopic analysis include thermal, chemical kinetic, and mineral data [22]. Fuel characteristics such as ultimate analysis, heating value, moisture content, particle size, bulk density, and ash fusion temperature of biomass have been reviewed [23]. Fuel properties for the combustion analysis of biomass can be conveniently grouped into physical, chemical, thermal, and mineral properties. Physical property values vary greatly and properties such as density, porosity, and internal surface area are related to biomass species whereas bulk density, particle size, and shape distribution are related to fuel preparation methods. Important chemical properties for combustion are the ultimate analysis, proximate analysis, analysis of pyrolysis products, higher heating value, heat of pyrolysis, heating value of the volatiles, and heating value of the char. Thermal property values such as specic heat, thermal conductivity, and emissivity vary with moisture content, temperature, and degree of thermal degradation by one order of magnitude. Thermal degradation products of biomass consist of moisture, volatiles, char and ash. Volatiles are further subdivided into gases such as light hydrocarbons, carbon monoxide, carbon dioxide, hydrogen and moisture, and tars. The yields depend on the temperature and heating rate of pyrolysis. Some properties vary with species, location within the biomass, and growth conditions. Other properties depend on the combustion environment. Where

Hazelnut shell Sawdust Corn stover Poplar Sugarcane bagasse Peach pit Rice husk Alfafa stalk Switchgrass

1.5 2.8 5.1 1.3 11.3 1.0 22.6 6.5 8.9

21.2 15.0 10.9 16.4 15.0 19.9 16.7 17.4 14.4

[32] [50] [51] [52] [52] [52] [53] [55] [55]

A. Demirbas / Progress in Energy and Combustion Science 30 (2004) 219230 Table 10 Inorganic properties of typical fuel samples (wt% of ash) Fuel sample Coal type 1 Coal type 2 Coal type 3 Red oak wood Wheat straw Walnut shell Almond shell Sunower shell Olive husk Hazelnut shell Source: Ref. [56]. Si2O 42.0 59.7 51.5 49.0 48.0 23.1 23.5 29.3 32.7 33.7 Al2O2 20.0 19.8 22.6 9.5 3.5 2.4 2.7 2.9 8.4 3.1 TiO2 1.2 2.1 2.0 0.1 0.1 0.1 0.3 0.1 Fe2O3 17.0 8.3 14.9 8.5 0.5 1.5 2.8 2.1 6.3 3.8 CaO 5.5 2.1 3.3 17.5 3.7 16.6 10.5 15.8 14.5 15.4 MgO 2.1 1.8 0.9 1.1 1.8 13.4 5.2 6.1 4.2 7.9 Na2O 1.4 0.8 1.0 0.5 14.5 1.0 1.6 1.5 26.2 1.3 K2O 5.8 2.1 2.0 9.5 20.0 32.8 48.5 35.6 4.3 30.4 SO3 5.0 2.0 3.5 2.6 1.9 2.2 0.8 1.3 0.6 1.1 P2O5 0.2 0.2 1.8 3.5 6.2 4.5 4.8 2.5 3.2

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Cl 0.8 3.6 0.1 0.2 0.2 0.2 0.1

the properties are highly variable, the likely range of the property is given [22]. 6.1. The chemistry of biomass combustion Combustion is a series of chemical reactions by which carbon is oxidized to carbon dioxide, and hydrogen is oxidized to water. In order to understand wood combustion, it is important to understand the properties of wood which determine its behavior as a fuel for combustion. Inuencing properties include anatomical structure and pathways for movement of moisture, moisture content, specic gravity, and holocellulose and lignin. Main combustion reactions are: Non-reacting solid ! Heat; drying ! PyrolysisVolatiles; Steam ! Precombustion reactions ! Primary gas phase combustion ! Secondary combustion ! Effluent stack gas 6.2. Some combustion properties of selected biomass samples Non-isothermal and isothermal thermogravimetric techniques have commonly been used to investigate the reactivities of carbonaceous materials [24 28]. A plot of the rate of weight loss against temperature while burning a sample under oxidizing atmosphere is referred to as burning prole [29]. The burning proles of sunower shell and pine cone samples are shown in Figs. 1 and 2. The rst peak, observed on the burning proles of the biomass samples corresponds to their moisture release. After releasing the moisture, some small losses in the mass of the sample occurred due to the desorption of the adsorbed gases. A sudden loss in the mass of the samples started at the temperatures between 450 500 K, representing the release of some volatiles and their ignition. In the rapid burning region, the rate of mass loss proceeded so rapidly that it reached to its maximum value. Rapid loss of mass immediately slowed down at the temperatures between 600 and 700 K. After then, burning

rate apparently decreased and consequently some small losses in the mass of the sample continuously went on as long as temperature was increased up to 1273 K, indicating the slow burning of the partly carbonized residue. At the end of hold time at 1273 K, samples reached to the constant weight after given periods [30]. The most important characteristic temperatures of a burning prole are ignition temperature and peak temperature [31]. The ignition temperature corresponds to the point at which the burning prole underwent a sudden rise. The ignition temperatures of samples were determined from their burning proles. As seen Table 11, the temperatures were determined as 475 K for sunower shell, 463 K for colza seed, 475 K for pine cone, 467 K for cotton refuse and 473 K for olive refuse [30]. The point on the burning prole at which is the rate of weight loss due to combustion is maximum known as peak temperature. The burning prole peak temperature is usually taken as a measure of the reactivity of the sample. These temperatures were found as 573 K for sunower shell, as 535 K for colza seed, as 565 K

Fig. 1. Burning prole of sunower shell (source: Ref. [30]).

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products of combustion because the water vapor was allowed to condense to liquid water. The HHV (in MJ/kg) of the biomass fuels as a function of xed carbon (FC, wt %) was calculated from Eq. (1) [32]: HHV 0:196FC 14:119 1

In earlier works [33,34], formulae were also developed for estimating the HHVs of fuels from different lignocellulosic materials, vegetable oils and diesel fuels using their chemical analysis data. For biomass fuels such as coal, the HHV was calculated using the modied Dulongs formula [33,35] as a function of the carbon, hydrogen, oxygen, and nitrogen contents from Eq. (2): HHV {33:5CC 142:3HC 2 15:4OC
Fig. 2. Burning prole of pine cone (source: Ref. [30]).

2 14:5NC} 1022

for pine cone, as 598 K for cotton refuses and as 537 K for olive refuse (Table 11). The rate of weight loss at the burning prole peak temperature is called the maximum combustion rate. The maximum combustion rates of the sunower shell, colza seed, pinecone, cotton refuse and olive refuse was calculated as 5.5, 2.8, 5.2, 3.7 and 3.4 mg/ min, respectively [30]. The weight loss percentages of ve different biomass samples versus temperature are illustrated in Fig. 3. From the Fig. 3, the weight losses of the samples increased sharply above 500 K. The weight loss differences between olive refuse and other samples started to increase above 620 K. Olive refuse has the lowest volatile matter content and the highest ash content; in other words, olive refuse has the lowest combustible part. The weight loss percentages of the sunower shell, colza seed, pinecone, cotton refuse and olive refuse at 1273 K were % 95.07, 91.05, 84.80, 86.74 and 78.69, respectively [30]. 6.3. Calculation of higher heating value The higher heating values (HHVs) or gross heat of combustion include the latent heat of the water vapor
Table 11 Some combustion properties of selected biomass samples Sample Ignition temperature (K) 417 423 463 423 438 Maximum combustion rate (mg/min) 5.50 2.80 5.20 3.70 3.40 Peak temperature (K) 573 535 565 598 537

where (CC) was carbon content (wt %), (HC), hydrogen content (wt %), (OC) oxygen content (wt %) and (NC), nitrogen content (wt %) The heat content is related to the oxidation state of the natural fuels in which carbon atoms generally dominate and overshadow small variations of hydrogen content. On the basis of literature values for different species of wood, Tillman [36] also found a linear relationship between HHV and carbon content. The HHVs of extractive-free samples reect the HHV of lignin relative to cellulose and hemicelluloses. It was reported that [37], cellulose and hemicelluloses (holocellulose) have a HHV of 18.60 kJ g21, whereas lignin has a HHV of 23.26 to 26.58 kJ g21. As discussed by Baker [38], HHVs reported for a given species reect only the samples tested and not the entire population of the species. The HHV of a lignocellulosic fuel is a function of its lignin content. In general, the HHVs of lignocellulosic fuels increase with increase of their lignin contents and the HHV is highly correlated with lignin content. For the model including the lignin content, the regression equation was HHV 0:0889LC 16:8218 3

Sunower shell Colza seed Pine cone Cotton refuse Olive refuse

Source: Ref. [30].

where LC was the lignin content (wt % daf and extractive-free basis). Again the heat content, which is a very important factor affecting utilization of any material as a fuel, is affected by the proportion of combustible organic components (called as extractives) present in it [39]. The HHVs of the extractive-free plant parts were found to be lower than those of the unextracted parts which indicate a likely positive contribution of extractives towards the increase of HHV. The Differential higher heating value (DHHV in MJ/kg) of the biomass samples as a function of extractive content (EC, wt %) can be

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Table 12 Physical properties and dry heating values of biomass and coal fuels Property Fuel density (kg/m3) Particle size Dry heating value (MJ/kg) Source: Ref. [56]. Biomass ,500 ,3 mm 16 Coal ,1300 ,100 mm 25

Fig. 3. Weight loss percentages of different biomass samples versus temperature Symbols for the biomass samples: B: Sunower shell, K: Colza seed, X: Pine cone, W: Cotton refuse, S: Olive refuse (Source: Ref: [30]).

calculated from Eq. (4): DHHV 0:383EC 2 0:0387 4

7. Coring of biomass and coal blends Coring refers to the combustion of biomass and coal for power production. Coring biomass with coal, in comparison with single coal ring, helps reduce the total emissions per unit energy produced. Coal and biomass fuels are quite different in composition. Coring biomass with coal has the capability to reduce both NOx and SOx levels from existing pulverized-coal red power plants. Coring may also reduce fuel costs, minimize waste and reduce soil and water pollution depending upon the chemical composition of the biomass used. The oldest of all fuels, wood (or biomass), and the old original fuel of the industrial revolution, coal, are key to this move to a new mission. Technical issues that can lead to doubt about of wood (or biomass) coring with coal are being resolved through testing and experience [6]. As such, the air pollution emissions accompanying the coal combustion are signicant. Among these pollutants are oxides of sulfur (SOx) and nitrogen (NOx), which lead to acid rain and ozone depletion. In addition, greenhouse gas emissions (CO2, CH4, etc.) have become a global concern [32]. Numerous methods have been proposed for reducing gaseous emissions of SO2, NOx and CO2 from fossil fuel combustion and for reducing costs associated with these mitigation techniques. Recent studies have shown that burning biomass with fossil fuels has a positive impact both on the environment and the economics of power generation [40 47]. The emissions of SO2 and NOx were reduced in most coring of biomass and coal techniques.

Biomass is much less dense and has signicantly higher aspect ratios than coal. It is also much more difcult to reduce to small sizes. Biomass that is cored with coal can be as much as 1/4 inch, sometimes more. These physical properties give rise to several interesting combustion issues (Table 12). The elemental composition differences between coal and biomass are indicated by the ultimate analyses (Table 13). Coal compositions vary with coal rank and geographic region, with two representative examples of a high-rank eastern coal and a low-rank western coal indicated here. It is difcult to establish a representative biomass due to large property variations, but two examples are included here for comparison. The composition variations among biomass fuels are larger than among coals, but as a class biomass has substantially more oxygen and less carbon than coal. Less obviously, nitrogen, chlorine, and ash vary signicantly among biomass fuels. These components are directly related to NOx emissions, corrosion, and ash deposition. Biomass generally has relatively low sulfur compared to coal. The inorganic properties of coal also differ signicantly from biomass (Table 14). Inorganic components in coal vary by rank and geographic region. As a class, coal has more aluminum, iron, and titanium than biomass. Biomass has more silica, potassium, and some times calcium than coal. A proximate analysis (Table 15), as dened by ASTM, is the determination by prescribed methods of moisture, volatile matter, xed carbon (by difference) and ash. 7.1. Co-pyrolysis Co-pyrolysis of carbonaceous material are complex function of the experimental conditions, under which the pyrolysis process proceeds. The most important factors, which affect the yield and composition of the volatile fraction liberated, are: coal rank or biomass type, maceral composition, particle size, temperature
Table 13 Ultimate analyses of typical fuel samples C Coal Red oak wood Wheat straw 81.5 50.0 41.8 H 4.0 6.0 5.5 N 1.2 0.3 0.7 S 3.0 Cl 1.5 Ash 7.0 1.3 15.0 O (diff.) 3.3 42.4 35.5

Source: Ref. [56].

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Table 14 Inorganic properties of typical fuel samples Si2O Coal Red oak wood Wheat straw 42.0 49.0 48.0 Al2O2 20.0 9.5 3.5 TiO2 1.2 Fe2O3 17.0 8.5 0.5 CaO 5.5 17.5 3.7 MgO 2.1 1.1 1.8 Na2O 1.4 0.5 14.5 K2O 5.8 9.5 20.0 SO3 5.0 2.6 1.9 P2O5 1.8 3.5 Cl 0.8 3.6

Source: Ref. [56]. Table 15 Proximate analyses of typical fuel samples Moisture (% of fuel) Coal Oak wood Wheat straw 4.8 ^ 2.6 6.5 ^ 0.8 7.3 ^ 1. Ash (% of dry fuel) 8.3 ^ 1.5 0.5 ^ 0.1 12.7 ^ 3.6 Volatile matter (% of dry fuel) 2.4 ^ 5.9 78.6 ^ 3.8 64.0 ^ 5.1 Fixed carbon (% of dry fuel) 43.6 ^ 3.8 21.5 ^ 2.1 23.4 ^ 2.5

Source: Ref. [56].

(i.e. temperature-time history), heating rate, atmosphere, pressure and reactor conguration. Co-pyrolysis of carbonaceous material divided into a hydrogen-rich volatile fraction, consisting of gases, vapors, and tar-components, and a carbon-rich solid residue. The pyrolysis process consists of a very complex set of reactions involving the formation of radicals. The radicals are very reactive and can undergo secondary reactions like cracking and carbon deposition, both inside and outside the particle. Stabilization of a radical, primarily via hydrogen addition, leads to a volatile component. The evolution of tar is controlled by mass transport in which the tar molecules evaporate into the light gas species and are carried out the particle at rates proportional to their vapor pressure and the volume of light gas. High pressure reduces the volume of light gases and hence reduces the yield of heavy molecules with low vapor pressure. Polymerization and condensation reactions, occurring via recombination of both volatile and nonvolatile radical components, result in the formation of the solid char particle. High pyrolysis heating rates produced chars with large macroporosites, more open pore structures, and larger macropore surface areas. Tar formation increases with increasing heating rate. The co-pyrolysis of the lignite sample and the biomass sample was resulted that the addition of lignite gave a slight synergistic effect in terms of increasing the oil yield from the hazelnut shell and also reduced the molecular weights of the resultant oil considerably. 7.2. Mechanism of biomass coring with coal A comparison of pyrolysis, ignition and combustion of coal and biomass particles reveals the following: 1. Pyrolysis starts earlier for biomass fuels compared to coal fuels.

2.

3. 4. 5. 6. 7.

The volatile material (VM) content of biomass (, 40%) is higher compared to that of coal (, 2 80%). The fractional heat contribution by VM in biomass is of the order of, 70% compared to, 36% for coal. Biomass char has more oxygen compared to coal. The heating value of volatiles is lower for biomass fuels compared to those from coal fuel. Pyrolysis of biomass chars mostly releases CO, CO2 and H2O. Biomass fuels have ash that is more alkaline in nature, which may aggravate the foulin problems.

8. Conclusion Biomass has a signicantly lower heating value than most coal. This is in part due to the generally higher moisture content and in part due to the high oxygen content. It was observed that the investigated biomass materials showed different combustion characteristics. The structural, proximate and ultimate analyses results of biomass and wastes differ considerably. Coring biomass with coal, in comparison with single coal ring, helps reduce the total emissions per unit energy produced. To reduce greenhouse gas emissions, the pressure is on conventional coal-red utilities to burn renewable fuels such as waste product or energy crop-derived biomass fuels as a lowest-cost option for reducing greenhouse gas emissions. Coal and biomass fuels are quite different in composition. Coring biomass with coal has the capability to reduce both NOx and SOx levels from existing pulverizedcoal red power plants. Coring may also reduce fuel costs, minimize waste and reduce soil and water pollution depending upon the chemical composition of the biomass

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used. Coring must be implemented with other approaches to provide a meaningful, long-term solution. Pyrolysis produces energy fuels with high fuel-to-feed ratios, making it the most efcient process for biomass conversion, and the method most capable of competing and eventually replacing non-renewable fossil fuel resources. The conversion of biomass to crude oil can be have an efciency of up to 70% for ash pyrolysis processes. The socalled biocrude can be used in engines and turbines. Its use as feedstock for reneries is also being considered. Some interesting trends have been obtained, especially with respect to the effect of net heating rate and temperature on the pyrolysis time. The reported literature results indicate a decrease in Final pyrolysis time as the net heating rate or temperature is increased [58].

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